Low temperature urethane curing agents

ABSTRACT

There is herein provided a urethane-containing material having one or more moieties of the structure: ##STR1## wherein R is hydrogen, an alkyl, alkenyl or aryl group; wherein X is hydrogen, an alkyl, alkenyl or aryl group, or wherein X is a moiety of the structure: ##STR2## of which R 1  and R 2  are, each independently, hydrogen, an alkyl, alkenyl or aryl group, or members of a cyclic or heterocyclic group. The urethane-containing material is particularly useful as a low temperature curing agent for active hydrogen-containing compositions.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel urethanes and to the methods ofmaking and using same. More specifically, the present invention relatesto novel urethanes which can be derived from isocyanates.

2. Brief Description of the Prior Art

Curable compositions containing blocked isocyanate crosslinking agentsare known in the art. Some of the crosslinking agents aid in effectingcure of these compositions at relatively low temperatures of about320°-350° F. (160°-177° C.) over a period of 20 to 30 minutes. Yet,lower temperature cure is required for coated substrates which haveplastic parts which tend to deform at the afore-stated temperatures.Hence, much work has been done to formulate compositions that cureeffectively at relatively lower temperatures.

As is the case here, much work has been done in developing blockedisocyanate crosslinking agents which would aid in effecting cure atlower temperatures. The work done has shown that proper selection ofblocking agents for isocyanate groups is determinative in effecting cureat low temperatures. It is believed that blocked isocyanates thatunblock readily at low temperatures effect cure of coatings at lowtemperatures. However, their use in coating compositions is limited insome respects. In one respect, coatings derived therefrom, althoughuseful, may have poor solvent resistance, indicating a relatively lowdegree of cure. In another respect, the coatings, although morecompletely cured, may have poor appearance. In yet another respect, someof these coating compositions, particularly the water-basedcompositions, are rather unstable.

By the present invention, a select group of blocking agents which aresuperior to blocking agents of the prior art have been found effectivein overcoming the afore-stated limitations.

SUMMARY OF THE INVENTION

In accordance with the foregoing, the present invention encompasses aurethane-containing material having a moiety of the structure: ##STR3##Preferably, R is hydrogen, an alkyl, alkenyl or aryl group, and X ishydrogen, an alkyl, alkenyl or aryl group, or a moiety of the structure:##STR4## Preferably, R₁ and R₂ are, each independently, hydrogen, analkyl, alkenyl or aryl group. In this context, the urethane-containingmaterial is alternately referred to as "novel urethane" or "blockedisocyanate".

In a method of preparing the novel urethane, an isocyanate is reactedwith a compound of the structure: ##STR5## wherein R and X are asdescribed above. This compound is alternately referred to herein as a"novel blocking agent".

A representative example of the above compound is a glycolamide such asN,N-dibutylglycolamide. This can be reacted with an isocyanate such as2,4-toluene diisocyanate to form the novel urethane. It has been foundthat the novel urethane is highly effective for low temperature cure ofcurable compositions such as coating compositions. In particular, it hasbeen found that the novel urethane is very suitable for low temperaturecure of water-based compositions such as electrodepositablecompositions. Notably, these compositions are stable and at relativelylow temperatures provide coatings of a high degree of cure, solventresistance, good appearance, as well as other known desirable filmproperties.

DETAILED DESCRIPTION OF THE INVENTION

The isocyanates which are useful in preparing the novel urethane can bemonoisocyanates or polyisocyanates, or a mixture thereof; thepolyisocyanates are preferred. They can be aliphatic or aromaticisocyanates, with the aromatic isocyanates being preferred for lowertemperature cure. Representative of the monoisocyanates areethylenically unsaturated monoisocyanate monomers such as vinylisocyanate, e.g., propenyl isocyanate, isopropenyl isocyanate, 9-decenylisocyanate; isocyanate acrylates, e.g., 2-isocyanato ethyl(meth)acrylate; allyl isocyanates, e.g., beta-allyloxyethyl isocyanate.These isocyanate monomers are typically reacted, i.e., blocked, with thenovel blocking agent and then copolymerized with appropriate monomersunder free radical polymerization conditions to form thermosettingcompositions.

Representative examples of the polyisocyanates are aliphatic isocyanatessuch as alkylene isocyanates, e.g., trimethylene, tetramethylene,pentamethylene, hexamethylene, 1,2-propylene, 1,2-butylene,2,3-butylene, 1,3-butylene, ethylidene and butylidene diisocyanates andthe cycloalkylene isocyanates, e.g., 1,3-cyclopentane, 1,4-cyclohexane,1,2-cyclohexane diisocyanates and isophorone diisocyanates.Representative examples of the polyisocyanates are aromatic isocyanatessuch as arylene isocyanates, e.g., m-phenylene, p-phenylene,4,4'-diphenyl, 1,5-naphthalene and 1,4-naphthalene diisocyanates andalkarylene isocyanates, e.g., 4,4'-diphenylene methane, 2,4- or2,6-tolylene, or mixtures thereof, 4,4'-toluidine, and 1,4-xylylenediisocyanates; nuclear-substituted aromatic compounds, e.g., dianisidinediisocyanate, 4,4'-diphenylether diisocyanate and chlorodiphenylenediisocyanate. Triisocyanates such as triphenylmethane-4,4',4"-triisocyanate, 1,3,5-triisocyanato benzene and2,4,6-triisocyanato toluene; and the tetraisocyanates such as4,4'-diphenyldimethyl methane-2,2',5,5'-tetraisocyanate and polymerizedpolyisocyanates such as tolylene diisocyanate dimers and trimers and thelike can also be used herein.

In addition, the polyisocyanates may be prepolymers derived from polyolssuch as polyether polyols or polyester polyols, including polyols whichare reacted with excess polyisocyanates, such as mentioned above, toform isocyanate-terminated prepolymers. Examples of the suitableisocyanate prepolymers are described in U.S. Pat. No. 3,799,854, column2, lines 22 to 53, which is herein incorporated by reference.

As afore-stated, in preparing the novel urethane of this invention, theisocyanate is reacted with the compound of the structure: ##STR6## R canbe hydrogen or a hydrocarbyl or substituted hydrocarbyl group, asaturated or unsaturated hydrocarbyl group such as an alkyl, alkenyl oraryl group. Examples of the alkyl groups are those containing from about1 to 10 and preferably 1 to 5 carbon atoms. Specific examples of thealkyl groups are methyl, ethyl, butyl, cyclopentyl and decyl groups.Examples of the alkenyl groups are those containing from about 2 to 10,and preferably from 2 to 5 carbon atoms. Specific examples of thealkenyl groups are ethenyl, propenyl, butenyl and cyclohexenyl groups.Examples of the aryl groups are those containing from about 6 to 30 andpreferably 6 to 15 carbon atoms. Specific examples of the aryl groupsare phenyl, benzyl, tolyl, xylyl and naphthyl groups. In theparticularly preferred embodiments of the invention, R is hydrogen or amethyl group.

X can be hydrogen or a hydrocarbyl or substituted hydrocarbyl group, asaturated or unsaturated hydrocarbyl group such as an alkyl, alkenyl oraryl group. Examples of the alkyl groups are those containing from about1 to 12 and preferably from about 6 to 12 carbon atoms. Specificexamples of the alkyl groups are methyl, ethyl, cyclopentyl, hexyl, anddodecyl groups. Examples of the alkenyl groups are those containing fromabout 2 to 12, preferably from 6 to 12 carbon atoms. Specific examplesof the alkenyl groups are ethenyl, propenyl, butenyl, hexenyl,cyclooctenyl, decenyl, 2,4-hexadienyl, 1,5-hexadienyl and4-methyl-1,5-pentadienyl groups. Examples of the aryl groups are thosecontaining from about 6 to 30 and preferably from about 6 to 15 carbonatoms. Specific examples of the aryl groups are benzyl, tolyl, xylyl andnaphthyl groups.

X can be the moiety of the structure: ##STR7## R₁ and R₂, eachindependently, can be hydrogen or a hydrocarbyl or substitutedhydrocarbyl group, a saturated or unsaturated hydrocarbyl group such asan alkyl, alkenyl or aryl group. Examples of the alkyl groups are thosecontaining from about 1 to 26, preferably from about 2 to 18, and morepreferably from about 4 to 8 carbon atoms. Specific examples of thealkyl groups are ethyl, propyl, butyl, pentyl, cyclohexyl, octyl, nonyl,decyl, dodecyl and stearyl groups. Examples of the alkenyl groups arethose containing from about 2 to 26, preferably from 2 to 18, and morepreferably from about 4 to 8 carbon atoms. Specific examples of thealkenyl groups are ethenyl, propenyl, butenyl, hexenyl, hexadecenyl andcyclooctenyl groups. Examples of the aryl groups can be those containingfrom about 6 to 30 and preferably 6 to 15 carbon atoms. Specificexamples of the aryl groups are phenyl, benzyl, tolyl, xylyl, andnaphthyl groups. R₁ and R₂ can be members of a cyclic or heterocyclicgroup such as morpholine, piperidine or the like.

Compounds possessing substantially the same properties as theunsubstituted hydrocarbyl groups exemplified above are equivalentsthereof and are those wherein the hydrocarbyl group can bear one or twoor more substituents. The substituents are such as would not adverselyaffect the reaction described herein or the utility of the invention.Non-limiting examples of the substituents are halo, e.g., fluoro andbromo; nitro; sulfato; alkoxy, e.g., methoxy, ethoxy, alkyl or alkenyl(as in aralkyl or aralkenyl), e.g., methyl, ethyl, butyl, propanol,butenyl and the like.

Specific examples of the afore-described compounds arehydroxyacetaldehyde, acetol, 1-hydroxy-2-butanone,α-hydroxyacetophenone, N,N-dipentylglycolamide, N,N-dipropylglycolamide,N,N-dibutyllactamide, N-methyllactamide, morpholine glycolamide,lactanilide, N,N-diethyllactamide, N-methyl-N-butyllactamide andN-octylglycolamide. Of these compounds, N,N-dibutylglycolamide isparticularly preferred.

As a matter of convenience, there is provided hereinbelow a suitablemethod of preparing the preferred glycolamides and glycollactamides.They can be prepared by reacting a corresponding acid (such as glycolicor lactic acid) or the ester thereof with an amine (such asdibutylamine). The amine is added to the acid or ester in a properlyequipped reaction vessel at temperatures of about 70°-170° C. Uponreaction, there is produced a water of reaction or alcohol which can beremoved by distillation. The resultant mixture may be vacuum stripped toremove the azeotropic solvent used therein and excess amine and/orunreacted acid or ester.

In preparing the novel urethane, the above compound and the isocyanateare admixed under anhydrous or substantially anhydrous conditions andgenerally in an inert atmosphere such as under a nitrogen blanket. Theequivalent ratio of the --NCO of the isocyanate to the --OH of the abovecompound can be from about 0.1 to 1.2:1.

Depending on the reagents employed, the starting materials may be addedsimultaneously to the reaction vessel, or they may be added slowly, oneto the other, at elevated temperature. After all the ingredients havebeen added, the mixture is reacted (with stirring) at a temperature andfor a period of time which depends, among others, on the isocyanate,until all, or virtually all of the isocyanate is reacted. For aromaticdiisocyanates, the reaction is carried out at about 25° and 100° C. forabout 1 to 8 hours, preferably, 35° to 80° C. for 1.5 to 5 hours. Foraliphatic diisocyanates, the reaction proceeds at about 50° to 100° C.for about 3 to 10 hours, preferably 80°-100° C. for 5 to 7 hours. Thedegree of conversion of the reactants to the urethanes can be determinedby infrared spectroscopy. It may, in some instances, be necessary toemploy other reactants such as alcohols to consume unreacted isocyanatesremaining in the resultant mixture.

A catalyst is usually employed in preparing the novel urethane.Catalysts useful herein are those suitable for urethane formation.Preferably, metals, metal salts or complexes, for example, lead acetate,dibutyltin dilaurate, stannous octoate and the like are employed.

A solvent is usually employed in preparing the novel urethane. Solventsthat are non-reactive with isocyanates are preferred, e.g., ketones,e.g., methyl isobutyl ketone, ethers such as diethyl ether of ethyleneglycols, or esters such as ethyl acetate, and other solvents such asdimethylformamide, dimethylsulfoxide, or N-methyl-2-pyrrolidone.

While the above method of preparing the novel urethane is describedherein with particularly, other methods of preparation can be employed.Thus, compounds or compositions obtained by other methods, havingstructural formula and properties as the novel urethane describedherein, are encompassed by this invention.

In the practice of the invention, the novel urethane is useful incombination with active hydrogen-containing materials to form curablecompositions such as coating compositions. In the preferred lowtemperature cure embodiments of the invention, the novel urethane isemployed with cure catalysts which are more fully defined herein. Theactive hydrogen group can be hydroxy, primary or secondary amino or thiogroup. Non-limiting examples of the active hydrogen-containing materialsare hydroxyl group-containing polymers, e.g., polymeric polyols, such asalkyd polymers, polyester polymers, hydroxyl group-containing acrylicpolymers, hydroxyl group-containing polyurethane polymers, hydroxylgroup-containing polyurea polymers, hydroxyl group-containing polyetherpolymers, hydroxyl group-containing epoxy polymers and hydroxylgroup-containing polymers which are polyepoxide-amine adducts. The epoxypolymers can be epoxy-free or epoxy-containing.

The molecular weights of the polymeric polyols can vary over a widerange depending upon their type and on whether the curable compositionis organic solvent based or water based and also on the desiredperformance characteristics of the coating. Polyester, epoxy and alkydpolymers can have molecular weights as low as about 500 and as high asabout 50,000, preferably the molecular weights are usually in the rangeof about 1,000 to 5,000; the molecular weights being on a number averagebasis relative to polystyrene, as determined by gel permeationchromatography. Acrylic polymers prepared by solution polymerization canhave molecular weights of about 100,000 or higher, and usually in therange of about 5,000 to 50,000 on a number average basis relative topolystyrene, as can be determined by gel permeation chromatography. Foracrylic latices, the molecular weight can range from 100,000 to severalmillions.

The hydroxyl content of the polymeric polyol should be sufficient suchthat when the polyol is in combination with the curing agent, thecomposition will cure to a solvent-resistant coating. Generally, thehydroxyl number of the polymeric polyol will be at least about 50 andpreferably will be in the range of about 100 to 300, based on resinsolids.

A preferred class of polymeric polyols are hydroxyl group-containingepoxy polymers. A particularly preferred class of polymeric polyols arethe polyepoxide-amine adducts. The epoxy polymers which can be used inthe practice of the invention are polyepoxides, that is, polymers havinga 1,2-epoxy equivalency greater than 1, preferably about 2 or more.Preferred are polyepoxides which are difunctional with regard to epoxy.The preferred polyepoxides are polyglycidyl ethers of cyclic polyols.Particularly preferred are polyglycidyl ethers of polyphenols such asbisphenol A. Examples of polyepoxides are given in U.S. Pat. No.4,260,716, column 3, line 20, to column 4, line 30, the portions ofwhich are hereby incorporated by reference.

Besides the epoxy polymers disclosed above, other epoxy-containingpolymers which can be used are acrylic polymers which contain epoxygroups. These polymers are formed by polymerizing an unsaturated epoxygroup-containing monomer such as glycidyl acrylate or methacrylate withone or more other polymerizable ethylenically unsaturated monomers.Examples of these polymers are described in U.S. Pat. No. 4,001,156,column 3, line 59, to column 5, line 60, the portions of which arehereby incorporated by reference.

Examples of amines which can be used in preparing the polyepoxide-amineadduct are ammonia, primary, secondary and tertiary amines and mixturesthereof. The reaction product of the polyepoxide and the amine can be atleast partially neutralized with an acid to form a polymeric productcontaining amine salt and/or quaternary ammonium salt groups. Reactionconditions of polyepoxides with amines, examples of various amines andat least partial neutralization with acid are disclosed in U.S. Pat. No.4,260,720, column 5, line 20, to column 7, line 4, the portions of whichare hereby incorporated by reference.

Also, various polyepoxide-amine adducts are described in European PatentApplication No. 0012463.

With regard to the amount of organic amine and polyepoxide which arereacted with one another, the relative amounts depend upon the extent ofcationic base such as cationic salt group formation desired and this inturn will depend upon the molecular weight of the polymer. The extent ofcationic salt group formation and the molecular weight of the reactionproduct should be selected such that when the resultant cationic polymeris mixed with aqueous medium, a stable dispersion will form. A stabledispersion is one which does not settle or is one which is easilydispersible if some sedimentation occurs. In some embodiments, thedispersion should additionally be of sufficient cationic character thatthe dispersed polymer particles will migrate towards the cathode when anelectrical potential is impressed between an anode and a cathodeimmersed in aqueous dispersion.

Also, the molecular weight, structure and extent of cationic salt groupformation should be controlled such that the dispersed polymer will havethe required flow to form a film on the substrate; in the case ofelectrodeposition, to form a film on the cathode. The film should beinsensitive to moisture to the extent that it will not redissolve in theelectrodeposition bath or be rinsed away from the coated surface afterremoval from the bath.

In general, most of the cationic polymers useful in the practice of theinvention will have average molecular weights within the range of about500-100,000 and contain from about 0.01 to 10, preferably about 0.1 to5.0, preferably from about 0.3 to 3.0 milliequivalents of basic group,e.g., cationic group, per gram of resin solids. Obviously one must usethe skill in the art to couple the molecular weight with the cationicgroup content to arrive at a satisfactory polymer. The polyglycidylethers will have molecular weights of about 500 to 10,000, preferably1,000 to 5,000. Acrylic polymers, on the other hand, will have molecularweights as high as 100,000, preferably 5,000 to 50,000.

Besides the cationic polymers, anionic polymers which are designed toform aqueous-based coating compositions may be used in coatingapplications such as electrodeposition. It should also be appreciatedthat organic solvent-based coating compositions employing the abovepolymers without ionic salt groups can also be used. Formulating coatingcompositions with such polymers is well known in the art and need not bedescribed in any further detail.

The novel urethane can be a separate or integral component to the activehydrogen-containing material. For example, a polyisocyanate can be fullyblocked with the novel blocking agent and be present as a separatecomponent with the active hydrogen-containing material. Alternately, apolyisocyanate can be partially blocked with the novel blocking agentand reacted with the active hydrogen-containing material to form anungelled one-component material. In the latter case, the resultanturethane is integral with the active hydrogen-containing material ratherthan being present as a separate component. Procedure for preparingintegral blocked isocyanate curing agents are shown in U.S. Pat. No.3,947,338. Whether present as a separate component or integral with theactive hydrogen-containing material, the novel urethane is present in anamount sufficient to impart excellent cure to the curable composition.Typically, the urethane is present in an equivalent ratio of 0.1:1 andpreferably 0.3 to 1:1 of the urethane to the active hydrogen-containingmaterial of the curable composition.

The novel urethane is usually employed in combination with a curecatalyst. Typically, the cure catalyst is a metal salt and/or complex ofa metal such as lead, zinc, iron, tin and manganese. Suitable salts ofthese metals are, for example, octoates and naphthanates. A suitablecomplex is, for example, acetyl acetonate. The cure catalyst is used inamounts sufficient to effect cure at the relatively low temperaturesdescribed herein. For example, the metal salt and/or complex is employedas a cure catalyst in amounts of about 0.1 to 2.0, preferably 0.2 to 1percent metal by weight (solids) based on the weight of the curablecomposition. The cure catalyst can be mixed simultaneously with otherstarting materials for the preparation of the coating composition, orintroduced into the coating composition in any order that is convenient.

In the practice of the invention, the curable compositions can be usedas coating, laminating or molding compositions. Preferably, they can beused as water-based or solvent-based coating compositions. Thecomponents of the coating composition can be mixed simultaneously or inany order that is convenient. If the components are a liquid and ofsufficiently low viscosity, they can be mixed together neat to form thecoating composition. Alternately, if the components are higher viscosityliquids or solids, the components can be mixed with a diluent to reducethe viscosity of the composition so that it may be suitable for coatingapplications.

By liquid diluent is meant a solvent or a non-solvent which is volatileand which is removed after the coating is applied and is needed toreduce viscosity sufficiently to enable forces available in simplecoating techniques, that is, brushing and spraying, to spread thecoating to controllable, desired and uniform thickness. Also, diluentsassist in substrate wetting, resinous component compatibility andcoalescence or film formation. Generally, when used, the diluent will bepresent in the composition in amounts of about 20 to 90, preferably 50to 80 percent by weight based on total weight of the coatingcomposition, although more diluent may be employed depending upon theparticular coating application.

Examples of suitable liquid diluents for organic solvent-based coatingswill depend somewhat on the particular system employed. In general,however, aromatic hydrocarbons such as toluene and xylene, ketones suchas methyl ethyl ketone and methyl isobutyl ketone, alcohols such asisopropyl alcohol, normal butyl alcohol, monoalkyl ethers of glycolssuch as 2-alkoxyethanol, 2-alkoxypropanol and compatible mixtures ofthese solvents can be used.

Besides organic solvents, water can be used as a diluent either alone orin combination with water-miscible organic solvents. When water is used,the coating composition is usually modified such as by incorporatingwater-solubilizing groups such as the cationic groups mentioned above toprovide for the necessary solubility in water. Besides the cationicgroups mentioned above, other water-solubilizing groups such asnon-ionic groups, for example, ethylene oxide groups, and anionic groupssuch as carboxylate salt groups may be introduced into the polymer todisperse or solubilize the coating composition in water.

The coating compositions of the invention may also optionally contain apigment. Pigments may be of any conventional type, comprising, forexample, iron oxides, lead oxides, strontium chromate, carbon black,coal dust, titanium dioxide, talc, barium sulfate, as well as colorpigments such as cadmium yellow, cadmium red, chromium yellow andmetallic pigments such as aluminum flake.

The pigment content of the coating composition is usually expressed asthe pigment-to-resin weight ratio. In the practice of the presentinvention, pigment-to-resin weight ratios can be 2:1 or higher, and formost pigmented coatings, are usually within the range of about 0.05 to1:1.

In addition to the above ingredients, various fillers, plasticizers,anti-oxidants, ultraviolet light absorbers, flow control agents,surfactants and other formulating additives can be employed if desired.These materials are optional and generally constitute up to 30 percentby weight of the coating composition based on total solids.

The coating compositions of the invention can be applied by conventionalmethods, e.g., non-electrophoretic methods including brushing, dipping,flow coating and spraying. Usually, they can be applied virtually overany substrate including wood, metal, glass, cloth, leather, plastic,foam and the like, as well as over various primers. Forelectroconductive substrates such as metals, the coatings can be appliedby electrodeposition. In general, the coating thickness will varysomewhat depending upon the application desired. In general, coatingsfrom about 0.1 to 10 mils can be applied and coatings from about 0.1 to5 mils are usual.

When aqueous dispersions of the coating composition are employed for usein electrodeposition, the aqueous dispersion is placed in contact withan electrically conductive anode and an electrically conductive cathode.The surface to be coated can be made the cathode or the anode. In thecase of cationic electrodeposition, which is preferred herein, thesurface to be coated is the cathode. Following contact with the aqueousdispersion, an adherent film of the coating composition is deposited onthe electrode being coated when a sufficient voltage is impressedbetween the electrodes. Conditions under which electrodeposition iscarried out are known in the art. The applied voltage may be varied andcan be, for example, as low as one volt or as high as several thousandvolts, but is typically between 50 and 500 volts. Current density isusually between 1.0 ampere and 15 amperes per square foot and tends todecrease during electrodeposition indicating the formation of aninsulating film.

After the coating has been applied, it is cured by heating at elevatedtemperatures for a period of time sufficient to form solvent-resistantcoatings. By solvent-resistant coatings is meant that the coating willbe resistant to acetone, for example, by rubbing across the coating withan acetone-saturated cloth. Coatings which are not cured or poorly curedwill not withstand the rubbing action with acetone and will be removedwith less than 10 acetone double rubs. Cured coatings, on the otherhand, will withstand a minimum of 20 acetone double rubs, and preferably100 acetone double rubs.

It has been found that substrates coated with compositions employing thenovel urethanes can cure at relatively lower temperatures. In certainembodiments of the invention, it has been found that the urethanesimpart excellent cure at temperature as low as 121° C. (250° F.). It isa feature of this invention that in comparison with conventional curingagents, particularly those which comprise blocked isocyanate curingagents, the urethanes impart a higher degree of cure at ordinary curetemperatures and at relatively lower temperatures. It is a distinctfeature of the invention that the novel urethanes are stable in coatingcompositions, particularly water-based coating compositions, and providelow temperature cure as described herein.

These and other aspects of the invention are illustrated morespecifically by the following non-limiting examples.

EXAMPLE 1

This example illustrates the preparation of N,N-dibutylglycolamide. Thefollowing were used in the preparation:

    ______________________________________                                        Ingredients         Parts by Weight (grams)                                   ______________________________________                                        Glycolic acid (70% technical grade)                                                               3091.5                                                    N,N--dibutylamine (reagent grade)                                                                 3538.1                                                    Toluene             356.6                                                     Toluene             213.8                                                     ______________________________________                                    

At room temperature, a properly equipped reaction vessel was chargedwith the glycolic acid, followed by addition of the N,N-dibutylaminethrough a dropping funnel at a rate slow enough to prevent boiling ofthe reaction mixture in the flask. The reaction temperature was keptpreferably below 70° C. so as to avoid loss of the amine. After theaddition, the reaction mixture was heated to reflux at 110° C., held forone hour at reflux, cooled to 95° C., and then the first portion oftoluene was added thereto. Thereafter, the reaction vessel was fittedwith a Dean-Stark trap containing toluene and then heated to 103° C. toremove water from the mixture. The removal of water through the trap wascontinued until the temperature reached 170° C. Upon cooling to 105° C.,the second portion of toluene was added. The mixture was again refluxedand water removed therefrom until the temperature reached 185° C. Theresultant mixture was then vacuum stripped to remove toluene and excessamine using a 23-inch of mercury vacuum and a maximum temperature of157° C. The resultant composition comprising N,N-dibutylglycolamide hada milliequivalent of acid per gram equal to 0.093, milliequivalent ofamine per gram equal to 0.07 and percent of water equal to 0.040.

EXAMPLE 2

This example illustrates the novel urethane and the method of preparingsame, using the above N,N-dibutylglycolamide and an isocyanate. Thepreparation was as follows:

    ______________________________________                                        Ingredients       Parts by Weight (grams)                                     ______________________________________                                        MONDUR TD-80.sup.1                                                                              522.0                                                       Methyl isobutyl ketone                                                                          469.4                                                       Trimethylolpropane                                                                              134.0                                                       Dibutyltin dilaurate                                                                            2 drops                                                     Dibutylglycolamide of Example 1                                                                 494                                                         2-Butoxyethanol   42.3                                                        Butanol           52.5                                                        ______________________________________                                         .sup.1 An 80/20 mixture of 2,4 and 2,6toluene diisocyanate, available fro     Mobay Chemical Company.                                                  

A solution of the diisocyanate and methyl isobutyl ketone was charged toa properly equipped reaction vessel at room temperature followed byaddition of the trimethylolpropane in 3 equal portions with the reactiontemperature being kept at about 40° C. Since the addition of thetrimethylolpropane was exothermic, each addition after the first one wasconducted after the exotherm had subsided. After adding all of thetrimethylolpropane, the reaction mixture was allowed to digest for about21/2 hours over the temperature range of 36°-40° C. Thereafter, and at40° C., the dibutyltin dilaurate was added to the reaction mixture.There was a mild exotherm with the temperature rising to 45° C.; theresultant mixture was held for about 3 hours at 45° C. until thetrimethylolpropane had been reacted. At 50° C., theN,N-dibutylglycolamide was added to the reaction mixture. The resultantmixture was held at 80° C. for about 6 hours to effect the reaction ofthe N,N-dibutylglycolamide and the isocyanate. The reaction was sampledand found to contain a small amount of isocyanate. The 2-butoxyethanolwas added to the reaction mixture and heated until only a small trace ofisocyanate was found to be present in the resultant mixture. Followingthis, the butanol was added to the resultant mixture. The resultantcomposition comprising the novel urethane had a solids content of 69.62percent.

EXAMPLE 3

This example illustrates the use of the novel urethane as a lowtemperature curing agent for coating compositions.

A low temperature-cure composition comprising an activehydrogen-containing material comprising a chain-extended adduct of anepoxy polymer and an amine (herein epoxy-amine adduct) was prepared asfollows:

    ______________________________________                                                           Parts by Weight                                                                           Equiva-                                        Ingredients        (grams)     lents                                          ______________________________________                                        EPON 828.sup.1     3623.8      19.2755                                        PCP-0200.sup.2     1286.9      4.8180                                         Xylene             316.3                                                      Bisphenol A        1098.7      9.6377                                         Benzyldimethylamine                                                                              7.7                                                        Benzyldimethylamine                                                                              13.5                                                       2-Ethoxyethanol    1123.8                                                     Diketimine derived from diethylene                                                               353.9       2.9492                                         triamine and methyl isobutyl ketone                                           (73% solids in methyl isobutyl                                                ketone)                                                                       N--methylethanolamine                                                                            284.5       3.7877                                         ______________________________________                                         .sup.1 Epoxy resin made from epichlorohydrin and bisphenol A having an        epoxy equivalent of 188, commercially available from Shell Chemical           Company.                                                                      .sup.2 Polycaprolactone diol having a molecular weight of 543, available      from the Union Carbide Corporation.                                      

The EPON 828, PCP-0200 and xylene were charged to a properly equippedreaction vessel and heated with a nitrogen sparge to 208° C. Thereaction was held at this temperature to reflux for about 1/2 hour toremove water via a Dean-Stark trap filled with xylene. The reactionmixture was cooled to 150° C. and the bisphenol A and the 7.7 parts byweight of the benzyldimethylamine (catalyst) were added. The reactionmixture was heated to 150°-190° C., held at this temperature for about1/2 hour and then cooled to 130° C. The 13.5 parts by weight of thebenzyldimethylamine catalyst were added and the reaction mixture held at130° C. for 21/2 hours until a reduced Gardner-Holdt viscosity (50percent resin solids solution in 2-ethoxyethanol) of P was obtained. The2-ethoxyethanol, methylethanolamine and diketimine were then added andthe mixture was held at 110° C. for 1 hour. The resultant product had asolids content of 79 percent.

The above epoxy-amine adduct was blended with the novel urethane ofExample 2 and formulated into a cationic paint as follows:

    ______________________________________                                        Ingredients         Parts by Weight (grams)                                   ______________________________________                                        The above epoxy-amine adduct                                                                      458                                                       The crosslinking agent of Example 2                                                               292                                                       DOWANOL PPH.sup.1   29                                                        Acetic acid         9.6                                                       Deionized water     2727.1                                                    Pigment paste.sup.2 235.0                                                     Catalyst paste.sup.3                                                                              14.8                                                      Cationic dispersant.sup.4                                                                         14.5                                                      ______________________________________                                         .sup.1 Phenoxypropanol, available from Dow Chemical Company.                  .sup.2 The pigment paste comprised deionized water, pigments and a            resinous pigment grinding vehicle as described in U.S. Pat. No. 4,007,154     (note Example II) which is incorporated herein by reference. The pigments     used therein were carbon black, lead silicate, strontium chromate and         aluminum silicate which were in a pigmentto-binder weight ratio of 2.5:1.     .sup.3 The catalyst paste comprised a dibutyltin oxide, deionized water       and the resinous pigment grinding vehicle described in footnote 2 above;      these ingredients were ground to a Hegman No. 7 grind.                        .sup.4 The cationic dispersant comprised a mixture of 120 parts of GEIGY      AMINE C (alkyl imidazole, commercially available from Geigy Industrial        Chemicals); 120 parts by weight of SURFYNOL 104 (acetylenic alcohol,          commercially available from Air Products and Chemicals Inc.); 120 parts b     weight of 2butoxyethanol, 221 parts by weight of deionized water and 19       parts by weight of glacial acetic acid.                                  

The cationic paint was prepared by blending the cationic resin, thecuring agent, the DOWANOL PPH and the cationic dispersant. The resultantcomposition was then neutralized with the acetic acid and dispersedslowly with the deionized water. The resultant composition was thenblended with the pigment paste and the catalyst paste. The resulantcomposition comprising the cationic paint had a pigment-to-binder weightratio of 0.2:1, a solids content of 20 percent and percentneutralization of 40.

The above cationic paint having a pH of 6.2 and bath conductivity of1110 μmhos/cm at 77° F. (25° C.) was used to electrocoat panels of coldrolled steel substrates at 275 volts for 2 minutes at a bath temperatureof 78° F. (26° C.). The electrocoated panels were baked at temperaturesof 250° F. (121° C.), 275° F. (135° C.) and 300° F. (149° C.) for 20minutes to obtain films of about 17.5 microns thickness. The baked filmswere hard and solvent resistant in that it took, respectively, 70, >100and >100 acetone double rubs to remove the films.

EXAMPLE 4

This example illustrates the novel urethane of this invention and themethod of preparing the same. The preparation entailed the reaction ofN,N-dipentylglycolamide with toluene diisocyanate.

N,N-dipentylglycolamide was prepared in essentially the same manner asdescribed in Example 1. The following were used in the preparation:

    ______________________________________                                        Ingredients         Parts by Weight (grams)                                   ______________________________________                                        Glycolic acid (70% technical grade)                                                               977.4                                                     N,N--dipentylamine  1427.4                                                    Toluene             112.5                                                     Toluene             67.6                                                      ______________________________________                                    

The resultant composition comprising the N,N-dipentylglycolamide had amilliequivalent of acid per gram of 0.036 and milliequivalent of baseper gram of 0.161.

The above N,N-dipentylglycolamide was reacted with a toluenediisocyanate to produce the urethane of this invention. The method ofpreparation was essentially the same as described in Example 2.

The following were used in the preparation:

    ______________________________________                                        Ingredients         Parts by Weight (grams)                                   ______________________________________                                        MONDUR TDS.sup.1    696.0                                                     Methyl isobutyl ketone                                                                            850.0                                                     Trimethylolpropane  178.9                                                     Dibutyltin dilaurate                                                                              0.06                                                      Dipentylglycolamide, afore-described                                                              860.0                                                     Butanol             94.4                                                      ______________________________________                                         .sup.1 2,4toluene diisocyanate, available from Mobay Chemical Company.   

The resultant composition comprising the urethane had a solids contentof 66 percent.

The above urethane was evaluated as a low temperature curing agent for acationic resin.

EXAMPLE 5

This example illustrates the novel urethane derived fromN,N-dibutyllactamide, and the method of preparing and using same.

N,N-dibutyllactamide was prepared in essentially the same manner asdescribed in Example 1, using the following:

    ______________________________________                                        Ingredients        Parts by Weight (grams)                                    ______________________________________                                        Lactic acid        1105.7                                                     N,N--dibutylamine (reagent grade)                                                                1408.2                                                     Toluene            132.0                                                      Toluene            100.0                                                      ______________________________________                                    

The resultant composition comprising N,N-dibutyllactamide had amilliequivalent of acid per gram of 0.077 and a milliequivalent of amineper gram of 0.118.

A urethane curing agent of the invention was prepared by reactingN,N-dibutyllactamide with a toluene diisocyanate. The following wereused in the preparation:

    ______________________________________                                        Ingredients       Parts by Weight (grams)                                     ______________________________________                                        MONDUR TDS        696.0                                                       Methyl isobutyl ketone                                                                          813.5                                                       Trimethylolpropane                                                                              178.7                                                       Dibutyltin dilaurate                                                                            0.06                                                        Dibutyllactamide, afore-described                                                               804.0                                                       Butanol           90.4                                                        ______________________________________                                    

The resultant composition comprising the urethane had a solids contentof 65 percent.

EXAMPLE 6

This example illustrates the novel urethane and the method of preparingsame, using N-octylglycolamide.

N-octylglycolamide was prepared in essentially the same manner asdescribed in Example 1, using the following:

    ______________________________________                                        Ingredients  Parts by Weight (grams)                                          ______________________________________                                        Glycolic acid                                                                              362.5                                                            Octylamine   450.0                                                            Toluene      41.8                                                             ______________________________________                                    

The resultant composition comprising N-octylglycolamide had amilliequivalent of acid per gram of 0.035 and a milliequivalent of amineper gram of 0.035.

A urethane of the invention was prepared by reacting theN-octylglycolamide with a toluene diisocyanate in essentially the samemanner as described in Example 2. The following were used in thepreparation:

    ______________________________________                                        Ingredients         Parts by Weight (grams)                                   ______________________________________                                        MONDUR TDS          261.0                                                     Methyl isobutyl ketone                                                                            327.7                                                     Trimethylolpropane  67.0                                                      Dibutyltin dilaurate                                                                              0.14                                                      N--octylglycolamide, afore-described                                                              266.5                                                     Butanol             10.0                                                      ______________________________________                                    

The resultant composition comprising the urethane had a solids contentof 58.6 percent.

EXAMPLE 7

This example illustrates the novel urethane and the method of preparingsame, using lactanilide.

Lactanilide was prepared using the following:

    ______________________________________                                        Ingredients   Parts by Weight (grams)                                         ______________________________________                                        Aniline       177.0                                                           Methyl lactate                                                                              198.5                                                           ______________________________________                                    

At room temperature, a properly equipped reaction vessel was chargedwith the aniline and the methyl lactate. The charged was heated under anitrogen blanket to reflux at 140° C. Infra-red spectral analysis of asample of the reaction mixture indicated formation of lactanilide.

Thereafter, the reaction vessel was fitted with a Dean-Stark trap andheated to remove methanol from the reaction mixture. Samples of thereaction mixture were analyzed to determine formation of lactanilide,and for that matter, the consumption of the reactants. After sufficientformation of lactanilide, the resultant mixture was vacuum stripped toremove unreacted aniline and methyl lactate. The resultant compositioncomprising lactanilide had a milliequivalent of acid per gram of 0.045and milliequivalent of amine per gram of 0.098.

A urethane of the invention was prepared by reacting the lactanilidewith a toluene diisocyanate in essentially the same manner as describedin Example 2. The following were used in the preparation:

    ______________________________________                                        Ingredients       Parts by Weight (grams)                                     ______________________________________                                        MONDUR TDS        111.0                                                       Methyl isobutyl ketone                                                                          100.0                                                       Trimethylolpropane                                                                              28.5                                                        Dibutyltin dilaurate                                                                            0.04                                                        Lactanilide, afore-described                                                                    95.5                                                        Methyl isobutyl ketone                                                                          135.8                                                       Ethylene glycol monobutyl ether                                                                 3.0                                                         ______________________________________                                    

The resultant composition comprising the urethane had a solids contentof 61.6 percent.

EXAMPLE 8

This example illustrates the novel urethane and the method of preparingsame, using morpholine amide of glycolic acid.

The morpholine amide of glycolic acid was prepared in essentially thesame manner as described in Example 1, using the following:

    ______________________________________                                        Ingredients  Parts by Weight (grams)                                          ______________________________________                                        Glycolic acid                                                                              721.3                                                            Morpholine   584.4                                                            Toluene      65.0                                                             Toluene      40.0                                                             ______________________________________                                    

The resultant composition comprising the morpholine amide of glycolicacid had a milliequivalent of acid per gram of 0.079 and amilliequivalent of amine per gram of 0.570.

A urethane of the invention was prepared by reacting morpholine amide ofglycolic acid with a toluene diisocyanate in essentially the same manneras described in Example 2. The following were used in the preparation:

    ______________________________________                                        Ingredients        Parts by Weight (grams)                                    ______________________________________                                        MONDUR TDS         360.0                                                      Methyl isobutyl ketone                                                                           270.1                                                      Trimethylolpropane 92.4                                                       Dibutyltin dilaurate                                                                             0.06                                                       Morpholine amide of glycolic acid, afore-described                                               300.0                                                      Methyl isobutyl ketone                                                                           135.1                                                      ______________________________________                                    

The resultant composition comprising the urethane had a solids contentof 62 percent.

EXAMPLE 9

This example illustrates the novel urethane and the method of preparingsame, using N-methyl-N-butyllactamide.

N-methyl-N-butyllactamide was prepared in essentially the same manner asdescribed in Example 1, using the following:

    ______________________________________                                        Ingredients      Parts by Weight (grams)                                      ______________________________________                                        Lactic acid (88%)                                                                              200.6                                                        N--methyl-N--butylamine                                                                        185.0                                                        Toluene          50                                                           Toluene          50                                                           ______________________________________                                    

The resultant composition comprising N-methyl-N-butyllactamide had amilliequivalent of acid per gram of 0.005 and a milliequivalent of amineper gram of 0.020.

A urethane of the invention was prepared by reactingN-methyl-N-butyllactamide with a toluene diisocyanate in essentially thesame manner as described in Example 2. The following were used in thepreparation:

    ______________________________________                                        Ingredients       Parts by Weight (grams)                                     ______________________________________                                        MONDUR TDS        111.0                                                       Methyl isobutyl ketone                                                                          240.0                                                       Trimethylolpropane                                                                              28.5                                                        Dibutyltin dilaurate                                                                            0.04                                                        N--methyl-N--butyllactamide                                                                     98.4                                                        Ethylene glycol monobutyl ether                                                                 90.4                                                        ______________________________________                                    

The resultant composition comprising the urethane had a solids contentof 61.6 percent.

EXAMPLE 10

This example illustrates the novel urethane and the method of preparingsame, using N,N-diethyllactamide.

N,N-diethyllactamide was prepared in essentially the same manner asdescribed in Example 7, using the following:

    ______________________________________                                        Ingredients   Parts by Weight (grams)                                         ______________________________________                                        Methyl lactate                                                                              300.0                                                           Diethylamine  231.4                                                           Diethylamine  50.0                                                            ______________________________________                                    

The resultant composition comprising N,N-diethyllactamide had amilliequivalent of acid per gram of 0.126 and a milliequivalent of amineper gram of 0.125.

A urethane of the invention was prepared by reactingN,N-diethyllactamide with a toluene diisocyanate in essentially the samemanner as described in Example 2. The following were used in thepreparation:

    ______________________________________                                        Ingredients          Parts by Weight (grams)                                  ______________________________________                                        MONDUR TDS           48.4                                                     Methyl isobutyl ketone                                                                             43.6                                                     Trimethylolpropane   12.5                                                     Dibutyltin dilaurate 0.02                                                     N,N--diethyllactamide, afore-described                                                             38.8                                                     Methyl isobutyl ketone                                                                             57.0                                                     Ethylene glycol monobutyl ether                                                                    2.4                                                      ______________________________________                                    

The resultant composition comprising the urethane had a solids contentof 69.7 percent.

EXAMPLE 11

This example illustrates the novel urethane and the method of preparingsame, using acetol. The following were used in the preparation:

    ______________________________________                                        Ingredients     Parts by Weight (grams)                                       ______________________________________                                        DESMODUR L2291.sup.1                                                                          1106.8                                                        ACETOL.sup.2    450                                                           Methyl isobutyl ketone                                                                        389.2                                                         ______________________________________                                         .sup.1 Aliphatic trifunctional isocyanate, available from Mobay Chemical      Company.                                                                      .sup.2 Hydroxyacetone, available from Jefferson Chemical Company.        

A properly equipped reaction vessel was charged with the DESMODUR. Thiswas followed by addition of the other ingredients, in the followingmanner. After adding 80 grams of the acetol, the mixture was heated to75° C. At 78° C., after about 225 grams of the acetol had been added,about 100 grams of the methyl isobutyl ketone was added to the mixture.At 80° C., another 100 grams of the methyl isobutyl ketone was added tothe mixture. Following this, the resultant mixture was cooled to 75° C.,and the rest of the acetol was added thereto. The resultant mixture wascooled and at 70° C., the remaining methyl isobutyl ketone was addedthereto. Infra-red spectral analysis of the resultant mixture showed noisocyanate. The resultant composition was thinned with an additional129.7 grams of methyl isobutyl ketone to produce a urethane compositionhaving a solids content of 75 percent.

The above urethane was used as a curing agent as follows:

    ______________________________________                                        Ingredients          Parts by Weight (grams)                                  ______________________________________                                        ACRYLOID AT 400.sup.1                                                                              114                                                      Acetol-derived urethane (from above)                                                               25                                                       Dibutyltin dilaurate 0.7                                                      ______________________________________                                         .sup.1 A hydroxy functional acrylic polymer available from Rohm and Haas.

The above ingredients were mixed well and the resultant composition wasdrawn down on bare steel substrates to produce a film. The film wasbaked at 350° F. (177° C.) to produce a hard, solvent-resistant filmwhich required 100 acetone double rubs to remove it.

EXAMPLE 12

The following example further shows the feature of the inventionrelating to the ability of the urethanes to impart high degree of cureto coating compositions at relatively low cure temperatures. The showingentailed a comparison of the urethanes of this invention with anart-related curing agent, in curing a solvent-based coating compositionat 275° F. (135° C.) for 30 minutes.

The urethanes used herein as curing agents were those describedrespectively in (i) Example 10 (derived from diethyllactamide), (ii)Example 9 (derived from N-methyl-N-butyllactamide) and (iii) Example 7(derived from lactanilide).

The coating compositions were prepared by admixing 80 grams of 50percent RJ100 in methyl isobutyl ketone (RJ100 is a copolymer of styreneand allyl alcohol, available from Monsanto Company), 0.6 gram of leadcure catalyst (CEM-ALL, available from Mooney Chemical Corp.) and therespective curing agent in an amount by weight (in grams) that wasrequired to provide 0.0059 equivalents of the blocked isocyanate.

COMPARATIVE EXAMPLE

A coating composition comprising an art-related curing agent (hereinreferred to as "control") was prepared in essentially the same manner asdescribed above, with the exception of the curing agent.

The art-related curing agent comprised the reaction product of an 80/20mixture of 2,4- and 2,6-toluene diisocyanate (3 moles),trimethylolpropane (1 mole) and ethylene glycol monobutyl ether (3moles) (70 percent solids in ethylene glycol monoethyl ether).

Evaluation: The coating compositions of Example 12 and the ComparativeExample were drawn down separately to form 3-mil films on differentparts of the same bare steel panel. The films were baked at 135° C.(275° F.) for 30 minutes and evaluated as to the degree of cure. Thedegree of cure was determined by measuring solvent resistance and by thenumber of acetone double-rubs needed to rub through the coating. Table Ibelow reports the results by identifying the cured coatings by theblocking agents of the respective curing agents.

                  TABLE I                                                         ______________________________________                                                           Degree of Cure,                                            Coating Containing Curing Agent                                                                  As Measured By Number                                      Having As A Blocking Agent:                                                                      of Acetone Double Rubs                                     ______________________________________                                        Ethylene glycol monobutyl ether (control)                                                         8                                                         Diethyllactamide   25                                                         N--methyl-N--butyllactamide                                                                      45                                                         Lactanilide        75                                                         ______________________________________                                    

EXAMPLE 13

The following example further shows the feature of the inventionrelating to the ability of the urethanes to impart high degree of cureto coating compositions at relatively low cure temperatures. The showingentailed a comparison of the urethanes of this invention with anart-related curing agent, in curing a water-based coating composition at250° F. (121° C.) for 30 minutes.

The novel urethanes used herein as curing agents were those describedrespectively in (i) Example 4 (derived from dipentylglycolamide), (ii)Example 1 (derived from dibutylglycolamide) and (iii) Example 5 (derivedfrom dibutyllactamide).

The water-based coating composition was prepared by admixing at 150° C.500 grams of epoxy-amine adduct as recited in Example 3 with equivalentamounts of the above urethanes. The amount of the urethane was theweight (in grams) that was required to give 0.55 equivalents of blockedisocyanate group. The resultant mixture was neutralized with 9.62 gramsof glacial acetic acid and thinned in deionized water to form an aqueousdispersion having a solids content of 35.5 percent. The 58 grams of curecatalyst paste as recited in Example 3 was added to the aqueousdispersion.

COMPARATIVE EXAMPLE

A coating composition comprising an art-related curing agent (hereinreferred to as "control") was prepared in essentially the same manner asdescribed in Example 13, with the exception of the curing agent.

The art-related curing agent comprised 274.4 grams of the reactionproduct of an 80/20 mixture of 2,4- and 2,6-toluene diisocyanate (3moles), trimethylolpropane (1 mole) and 2-ethylhexanol (3 moles) (70percent solids in ethylene glycol monoethyl ether).

Evaluation: The coating composition of Example 13 and the ComparativeExample were drawn down separately to form 3-mil films on differentparts of the same bare steel panel. The films were baked at 250° F.(121° C.) for 30 minutes and evaluated as to the degree of cure. Thedegree of cure was determined by measuring solvent resistance by thenumber of acetone double rubs needed to rub through the coating. TableII below reports the results by identifying the cured coatings by theblocking agents of the respective curing agents.

                  TABLE II                                                        ______________________________________                                                           Degree of Cure                                             Coating Containing Curing Agent                                                                  As Measured By Number                                      Having As A Blocking Agent:                                                                      of Acetone Double Rubs                                     ______________________________________                                        2-Ethylhexanol (control)                                                                          3                                                         (i) Dipentylglycolamide                                                                          60                                                         (ii) Dibutylglycolamide                                                                          40                                                         (iii) Dibutyllactamide                                                                           30                                                         ______________________________________                                    

EXAMPLE 14

This example further illustrates the method of cationicelectrodeposition of coating compositions containing the novelurethanes.

A cationic paint was formulated and electrocoated, as follows:

    ______________________________________                                        Ingredients       Parts by Weight (grams)                                     ______________________________________                                        The novel urethane of Example 5                                                                 354.4                                                       (derived from dibutyllactamide)                                               Epoxy-amine adduct*                                                                             1500.0                                                      Glacial acetic acid                                                                             9.6                                                         Deionized water   883.3                                                       Deionized water   1704.6                                                      Cure catalyst paste*                                                                            293.5                                                       Pigment paste*    13.9                                                        ______________________________________                                         *This ingredient is the same as described in Example 3.                  

The epoxy-amine adduct was heated to 100° C. and mixed with the novelurethane. To the mixture was added the glacial acetic acid to effectneutralization thereof. The resultant mixture was thinned in the firstportion of water to form an aqueous dispersion having a solids contentof 35.5 percent. The dispersion was further thinned in the secondportion of water.

To 1610 grams of the resultant aqueous dispersion were added the pigmentand catalyst pastes and mixed to form a cationic paint having a solidscontent of 20 percent, a pigment-to-binder ratio of 0.2:1 and percentneutralization of 40.

The above paint, at a pH of 6.45 and bath conductivity of 1200 μmhos/cmand a bath temperature of 78° F. (26° C.), was used to electrocoat baresteel panels at 300 volts for 2 minutes. The electrocoated panels werebaked at 275° F. (135° C.) to produce films of 17.5 microns thickness.The baked films were hard and solvent-resistant films, in that it took60 acetone double rubs to remove the films.

EXAMPLE 15

This example also illustrates the method of cationic electrodepositionof coating compositions containing the novel urethanes. A cationic paintwas formulated and electrocoated in essentially the same manner asdescribed in Example 14, with the exception that the novel urethane usedherein was as described in Example 4 (derived from dipentylglycolamide).

The following were used in the preparation:

    ______________________________________                                        Ingredients        Parts by Weight (grams)                                    ______________________________________                                        The novel urethane of Example 4                                                                  366.2                                                      (derived from dipentylglycolamide)                                            Epoxy-amine adduct 500.0                                                      Glacial acetic acid                                                                              9.6                                                        Deionized water    893.2                                                      Deionized water    1556.5                                                     Cure catalyst paste                                                                              222.3                                                      Pigment paste      12.7                                                       ______________________________________                                    

The cationic paint had a solids content of 20 percent, apigment-to-binder ratio of 0.2:1 and percent neutralization of 40.

The above paint, at a pH of 6.1, bath conductivity of 960 μmhos/cm, andbath temperature of 80° F. (27° C.) was used to electrocoat bare steelpanels at 50 volts for 2 minutes to produce films of 15 microns. Theelectrocoated panels were baked at 275° F. (135° C.) for 20 minutes toproduce hard and solvent-resistant films, in that it required 75 acetonedouble rubs to remove them.

Therefore, what is claimed is:
 1. A urethane-containing material havingone or more moieties of the structure: ##STR8## wherein R is hydrogen,an alkyl, alkenyl or aryl group; wherein X is hydrogen, an alkyl,alkenyl or aryl group, or wherein X is a moiety of the structure:##STR9## of which R₁ and R₂ are, each independently, hydrogen, an alkyl,alkenyl or aryl group, or members of a cyclic or heterocyclic group. 2.A urethane-containing material of claim 1, wherein R is hydrogen, analkyl, alkenyl or aryl group.
 3. A urethane-containing material of claim2, wherein the alkyl group contains from about 1 to 10 carbon atoms. 4.A urethane-containing material of claim 3, wherein the alkyl groupcontains from about 1 to 5 carbon atoms.
 5. A urethane-containingmaterial of claim 2, wherein R is hydrogen or a methyl group.
 6. Aurethane-containing material of claim 1, wherein the moiety ##STR10## ofwhich R₁ and R₂ are, each independently, hydrogen, an alkyl, alkenyl oraryl group, or members of a cyclic or heterocyclic group.
 7. Aurethane-containing material of claim 6, wherein the alkyl groupcontains from about 1 to 26 carbon atoms.
 8. A urethane-containingmaterial of claim 7, wherein the alkyl group contains from about 2 to 18carbon atoms.
 9. A urethane-containing material of claim 8, wherein thealkyl group contains from about 4 to 8 carbon atoms.
 10. A blockedisocyanate obtained by reacting:(A) an isocyanate, and (B) a compound ofthe structure: ##STR11## wherein R is hydrogen, an alkyl, alkenyl oraryl group; wherein X is hydrogen, an alkyl, alkenyl or aryl group, orwherein X is a moiety of the structure: ##STR12## of which R₁ and R₂are, each independently, hydrogen, an alkyl, alkenyl or aryl group, ormembers of a cyclic or heterocyclic group.
 11. A compound as recited inclaim 10, wherein the moiety X is ##STR13## of which R₁ and R₂ are, eachindependently, hydrogen, an alkyl, alkenyl or aryl group, or members ofa cyclic or heterocyclic group.
 12. A compound of claim 11, wherein thealkyl group contains from about 1 to 26 carbon atoms.
 13. A compound ofclaim 12, wherein the alkyl group contains from about 2 to 18 carbonatoms.
 14. A compound of claim 13, wherein the alkyl group contains fromabout 4 to 8 carbon atoms.
 15. A compound of claim 10, wherein R ishydrogen, an alkyl, alkenyl or aryl group.
 16. A compound of claim 15,wherein the alkyl group contains from about 1 to 10 carbon atoms.
 17. Acompound of claim 16, wherein the alkyl group contains from about 1 to 5carbon atoms.
 18. A compound of claim 15, wherein R is hydrogen or amethyl group.
 19. A compound of claim 10, which isN,N-dibutylglycolamide, N,N-dipentylglycolamide, N,N-dibutyllactamide oranilide.
 20. A blocked isocyanate of claim 10 in which the isocyanate isa polyisocyanate.
 21. A blocked isocyanate of claim 10, wherein theisocyanate is aromatic.